Phosphonylated derivatives of aliphatic heterochain and acrylate polymers and applications thereof

ABSTRACT

A variety of phosphonylated heterochain polymers are disclosed, including, most preferably, phosphonylated polymethyl methacrylate. For each polymeric composition the phosphorous atom of a phosphorous-containing functional group is covalently bonded to a carbon atom of the polymeric chain. The phosphorous atoms are present in an amount of at least about 0.1 percent by weight in each polymeric composition.

BACKGROUND TO THE INVENTION

[0001] Phosphonylation of organic compounds and polymers has beendocumented in the prior art. Early applications focused on massphosphonylation of non-functional polymers to introduce phosphonylategroups randomly along their carbon chain by allowing a solution of thesepolymers in phosphorous trichloride to interact with gaseous oxygen(U.S. Pat. No. 3,097,194; U.S. Pat. No. 3,278,464). For example, U.S.Pat. No. 3,097,194 to Leonard is directed to a process for preparingelastomeric phosphonylated amorphous copolymers of ethylene andpropylene which are essentially free of low molecular weight polymeroils. Phosphorylation, or esterification of the copolymer, is conductedin situ of the copolymer solution mass after inactivating apolymerization catalyst with water and oxygen to convert the catalyst toan inert metal oxide. Oxygen is then bubbled through the reaction massin the presence of phosphorous trichloride to obtain the phosphorylatedcopolymer.

[0002] An example of phosphonated polymers is provided in U.S. Pat. No.3,278,464 to Boyer et al. In accordance therewith, ethylenicallyunsaturated polymers are reacted with an organic-substituted phosphorouscompound to produce phosphonated polymers. Like the process describedabove, attachment of the phosphorous groups results in near-homogeneous,or mass, phosphonylation within the polymer and phosphorous compoundsare combined in a solvent system.

[0003] Moreover, in U.S. Pat. No. 4,207,405 to Masler et al.,polyphosphates are provided that are the homogeneous reaction products,in an organic solvent, of phosphorous acid or phosphorous trichlorideand a water-soluble carboxyl polymer. U.S. Nat. No., 3,069,372 toSchroeder et al., U.S. Pat. No. 4,678,840 to Fong et al., U.S. Pat. No.4,774,262 to Blanquet et al., U.S. Pat. No. 4,581,415 to Boyle Jr., etal., and U.S. Pat. No. 4,500,684 to Tucker show variousphosphorous-containing polymer compounds.

[0004] U.S. Pat. Nos. 4,814,423 and 4,966,934 to Huang et al., describeadhesives for bonding polymeric materials to the collagen and calcium ofteeth. For bonding to calcium, the adhesive employs an ethylenicallyunsaturated polymeric monophosphate component. A tooth is coated withthe adhesive and then a filling is applied.

[0005] More recently, restricting the phosphonylation to the surface ofpolymeric substrates was achieved to produce articles withsurface-phosphonylate functionalities and practically intact bulk (U.S.Pat. Nos. 5,491,198 and 5,558,517 to Shalaby et al.). This was achievedby gas phase phosphonylation of a preformed article with PCl₃ and O₂ orpassing through a solution of PCl₃ in a non-reactive organic liquid thatis also a non-solvent for the polymeric article. In effect, a processfor phosphonylating the surface of an organic polymeric preform and thesurface-phosphonylated preforms produced thereby are provided. Organicpolymeric preforms made from various polymers including polyethylene,polyether-ether ketone, polypropylene, polymethyl methacrylate,polyamides and polyester, and formed into blocks, films, and fibers mayhave their surfaces phosphonylated according to that process. Theprocess involves the use of a liquid medium that does not dissolve thisorganic polymeric preform but does dissolve a phosphorous halide such asphosphorous trichloride, and the like. The process allows for surfacephosphonylation of the organic polymeric preform such that up to about30 percent but preferably up to about 20 percent, of the reactive carbonsites in the polymer are phosphonylated. The phosphonylated organicpolymers are particularly useful as orthopedic implants becausehydroxyapatite-like surfaces which can be subsequently created on theorganic implants allow for co-crystallization of hydroxyapatite to formchemically bound layers between prosthesis and bone tissue.

[0006] Although various phosphonylated polymers are known, the prior artis deficient in affording phosphorous-containing groups randomly andcovalently attached to carbon atoms of aliphatic chains and pendant sidegroups of organo-soluble polymers such as polyalkylene oxides,polyamides, polyesters, and acrylate polymers, that are tailored for usein specified technology areas.

SUMMARY OF THE INVENTION

[0007] In one aspect the present invention is directed to a randomlyphosphonylated acrylate polymeric composition which includes an acrylicpolymer and phosphorous-containing functional groups, wherein thephosphorous atom of each functional group is covalently bonded to acarbon atom of the acrylic polymer and wherein the phosphorous atomscomprise at least about 0.1 percent by weight of the polymericcomposition.

[0008] Preferably, the acrylic polymer is polymethyl-methacrylate andthe phosphorous atoms comprise at least 0.5 percent by weight of thepolymeric composition. Optionally, the acrylic polymer is based onmethyl-methacrylate and methacrylic acid repeat units. It is also withinthe scope of the present invention that the acrylic polymer includes atleast one polymerizable side group per chain, preferably a group derivedfrom a bis-acrylate monomer, most preferably, ethylene bis-methacrylate.

[0009] A preferred application for the phosphonylated acrylate polymericcomposition of the present invention is as a dental product such as avarnish or sealer, preferably one which includes fluoride ions which maybe released on a controlled manner. It is also desirable that the dentalproduct made in accordance with the present invention includes bioactivecompounds such as antimicrobials, anti-inflammatory drugs, orpain-relieving agents, with the polymeric composition being capable ofregulating the release of the bioactive compounds.

[0010] In another aspect the present invention is directed to a randomlyphosphonylated polyalkylene oxide polymeric composition which includes apolyalkylene oxide polymer and phosphorous-containing functional groups,wherein the phosphorous atom of each of the functional groups iscovalently bonded to a carbon atom of the polyalkylene oxide polymer andwherein the phosphorous atoms comprise at least about 0.1 percent byweight of the polymeric composition. Preferably the alkylene group ofthe polyalkylene oxide polymer has from two to six carbon atoms.

[0011] In yet another aspect the present invention is directed to arandomly phosphonylated polyamide composition which includes a polyamidepolymer and phosphorous-containing functional groups, wherein thephosphorous atom of each of the functional groups is covalently bondedto a carbon atom of the polyamide polymer and wherein the phosphorousatoms comprise at least about 0.1 percent by weight of the composition.Preferably, the polyamide is the polymerization product of N-alkyllaurolactam.

[0012] In a still further aspect the present invention is directed to arandomly phosphonylated polyester composition which includes a polyesterpolymer and phosphorous-containing functional groups, wherein thephosphorous atom of each of the functional groups is covalently bondedto a carbon atom of the polyester polymer and wherein the phosphorousatoms comprise at least about 0.1 percent by weight of the composition.Preferably the polyester is poly-ε-caprolactone. The present polyestercomposition is especially useful as a flame retardant additive forpolyesters and polyurethanes.

[0013] All of the present inventive polymeric compositions may include abioactive compound linked to the phosphonyl functionality.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention deals with novel phosphonylated derivativesof polyalkylene oxides, N-substituted aliphatic polyamides, and acrylatepolymers, and preferably, specifically, polyethylene oxide (PEO),N-ethyl, Nylon 12 (N-12) [description of alkylated N-12 can be found inShalaby et al., J. Polym. Sci.-Polym. Phys. Ed., 11,1 (1973)], andpolymethyl methacrylate (PMMA). Generally, the phosphonylation of therepresentative members of these groups of polymers occurs by bubblingoxygen through a polymer solution in PCl₃ with or without a non-reactiveorganic solvent. The resulting phosphonyldihalide-bearing polymers maythen be converted to corresponding phosphonic acid and its metal salts,amides, imides, or esters. Conversion to (1) phosphonic acid is achievedby reacting with water in the presence or absence of an acidic or basiccatalyst (followed by acidification); (2) amides by reacting with anamine; (3) imides by reacting with a primary or secondary amide (as inthe case of the sodium salt of ε-caprolactam); and (4) esters byreacting with an alcohol or phenol.

[0015] A preferred composition of the present invention is aphosphonylated PMMA having more than 0.1 percent phosphorous, present asphosphonic acid functionality, with the phosphonic acid being thedominant phosphonyl functionality. Another preferred composition of thisinvention is a derivative of the phosphonylated PMMA wherein the methylester groups of PMMA are partially or fully hydrolyzed [that take placeduring the hydrolysis of —P(O)Cl₂ to P(O)(OH)₂] are reacted (esterified)with a glycidyl acrylate (such as glycidyl methacrylate) to introduce apolymerizable acrylic side group onto the phosphonylated PMMA (PPMMA)chain. Another preferred composition of this invention is the reactionproduct of the PMMA [through the —P(O)Cl₂ functionality] withhydroxyethyl methacrylate (through the —OH group) to yield a product(PMH) having a phosphonate ester side group with a polymerizable acrylicfunctionality. Another preferred composition of this invention is aphosphonylated polyethylene oxide (OPPO) having more than 0.1 percentphosphorous present primarily as phosphonic acid groups, phosphonyldichloride and their respective derivative with hydroxy- oramine-bearing bioactive compounds. Another preferred composition of thisinvention is a phosphonylated N-alkylated Nylon 12 and more preferablyN-ethyl Nylon 12 having more than 0.1 percent phosphorous presentprimarily as phosphonic acid. Another preferred composition of thisinvention is a derivative of the phosphonylated N-ethyl Nylon-12,wherein the initial phosphonyl dihalide groups are reacted with sodiumε-caprolactam [using a similar process to that described by Shalaby andReimschuessel, J. Polym. Sci.-Polym. Chem. Ed., 15, 251 (1977)]. Anotherpreferred composition of this invention is phosphonylated polyester andmore preferably poly-ε-caprolactone having more than 0.1 percent P asfree phosphonic acid or dialkyl phosphonate groups. The latter can beprepared by reacting the initial phosphonylation product bearingphosphonyl dihalide groups with an alcohol such as ethanol or methanol.

[0016] Of the many possible applications of the new compositions subjectof this invention, the following are representative systems:

[0017] 1. Phosphonylated PMMA and Derivatives

[0018] These can be used in several dental applications pertinent to (a)desensitizing through interaction with Ca⁺² in the biologic environmentto seal the teeth surface and fill the micro-channel with an insolublepolymeric salt; (b) increasing the impact strength of dental fillersthrough ionic binding of the polymeric chain that acts as an impactmodifier; (c) increasing the impact strength of cement ionomers throughthe ionic binding of the impact modifying polymer; (d) pretreating thesurface of dentine for improved adhesion to dental filling; (e)surface-coating to provide an adherent dental varnish or a controlledrelease system for fluorides and other dental agents for treatinginfections (including microbial ones) or pain; and (f)interfacial-bonding of phosphonylated fibers to a methacrylate-basedmatrix for producing high impact dental composites.

[0019] 2. Phosphonylated Polyethylene Oxides (PEO) and Derivatives

[0020] These can be used as drug carriers in different controlledrelease systems, such as those used in transdermal delivery with orwithout employing an iontophoretic scheme. Other uses of the PEOphosphonic acid derivatives can include those pertinent to coldsterilization and disinfection. Phosphonylated derivatives bearingphosphonyl dihalide groups can be used for covalently binding hydroxy-and/or amine-bearing bioactive compounds for their controlled release.Yet another application of phosphonic acid derivatives include their useas polyelectrolytes for flocculation. The phosphonic acid-bearing systemcan be used as a carrier of cationic drugs for controlling their releasein oral, intranasal, intravaginal, or transdermal pharmaceuticalformulations. The phosphonylated PEO can be used as a foam forprotecting flammable objects exposed to an open flame.

[0021] 3. Phosphonylated N-ethyl Nylon 12 and Derivatives

[0022] N-ethyl Nylon 12 with practically all the phosphonyl moietiespresent as phosphonic acid groups can be used as polymeric catalysts forthe hydrolytic polymerization of lactams. The derivatives of thephosphonylated polymer carrying N-substituted ε-caprolactam group can beused as a co-catalyst for the anionic polymerization of lactams intocomb-shaped or crosslinked structures.

[0023] 4. Phosphonylated Poly-ε-Caprolactone and Its Derivatives

[0024] These can be used as primers for metallic fibers in polymericcomposite applications. The alkyl-phosphonate groups can be used asflame-retarding additives for polyesters and polyurethanes.

[0025] Specific examples for the preparation of representativecompositions are given below.

EXAMPLE 1 Phosphonylation of Low Molecular Weight PolymethylMethacrylate

[0026] A two-neck 250 ml boiling flask containing a magnetic stir barwas assembled with a condenser in one inlet and a gas inlet tube in theother. The set up was flame dried under vacuum and cooled to roomtemperature under argon purge twice. Twenty grams of low molecularweight polymethyl methacrylate (PMMA) and 50 ml chloroform was added tothe boiling flask. Once the PMMA was completely dissolved, 20 mlphosphorus trichloride was added to the solution. Oxygen was bubbledthrough the solution at 30 ml/min while stirring with the magnetic stirbar. The oxygen flow and stirring were continued at ambient temperaturefor 73 hours.

[0027] The condenser and gas inlet tube were removed from the flask andreplaced with a full length glass stopper and 90° angle connector withstopcock. The system was placed under vacuum while stirring to removethe chloroform. Once the solvent was removed, the flask was purged flaskwith argon and 100 ml acetone was added to dissolve the material in theflask. After the residue was dissolved, 37 ml of 0.5 M HCl was added tothe solution. After 48 hours, the solution was precipitated by blendingin distilled ice water for 2 minutes. The precipitate was collected byfiltering through a coarse Buchner funnel.

[0028] The precipitate was added to 500 ml distilled water and sonicatedfor 1 hour. The mixture was filtered through a coarse Buchner funnel,and the precipitate was collected. The precipitate was mixed with 250 mldistilled water and incubated at 37° C. for 1 hour. The water wasdecanted water, 250 ml distilled water was added, and the mixture wasincubated at 37° C. for 1 hour; repeated fifteen times. The mixture wasfiltered through a coarse Buchner funnel. The precipitate was collectedand dried under vacuum at 37° C. for 12 hours. The composition andproperties of the polymer were determined by elemental analysis, dilutesolution viscometry, titration, NMR, and IR spectroscopy.

EXAMPLE 2 Phosphonylation of Medium Molecular Weight PMMA

[0029] A two-neck 250 ml boiling flask containing a magnetic stir barwas assembled with a condenser in one inlet and a gas inlet tube in theother. The set up was flame dried under vacuum and cooled to roomtemperature under argon purge twice. Twenty grams of medium molecularweight PMMA and 100 ml chloroform was added to the boiling flask. Oncethe PMMA was completely dissolved, 20 ml phosphorus trichloride wasadded to the solution. Oxygen was bubbled through the solution at 30ml/min while stirring with the magnetic stir bar. The oxygen flow andstirring were continued at ambient temperature for 91 hours.

[0030] The condenser and gas inlet tube were removed from the flask andreplaced with a full length glass stopper and 90° angle connector withstopcock. The system was placed under vacuum while stirring to removethe chloroform. Once the solvent was removed, the flask was purged flaskwith argon and 100 ml acetone was added to dissolve the material in theflask. The solution was precipitated by blending in distilled ice waterfor 2 minutes. The precipitate was collected by filtering through acoarse Buchner funnel.

[0031] The precipitate was mixed with 250 ml distilled water andincubated at 37° C. for 1 hour. The water was decanted water, 250 mldistilled water was added, and the mixture was incubated at 37° C. for 1hour; repeated twenty-three times. The mixture was filtered through acoarse Buchner funnel. The precipitate was collected and dried undervacuum at 37° C. for 12 hours. The composition and properties of thepolymer were determined as described in Example 1.

EXAMPLES 3-23

[0032] Twenty additional phosphonylated PMMA derivatives are preparedusing similar or slightly modified reaction conditions andcharacterization methods as those described in Examples 1 and 2. Asummary of the prevailing reaction conditions and analysis (for %P) ofthe re presented in Table I. TABLE I Reaction Conditions and Propertiesof Resulting Products Product PCl₃ Rxn Example Number PMMA* * Solvent(ml) Time (hr.) % P  1 PM-9 20 g Low MW  50 ml chloroform 20 73 1.45  2PM-10 20 g Medium MW 100 ml chloroform 20 91 1.88  3* PM-1  5 g MediumMW  15 ml chloroform 5 21 6.24  4* PM-2 S-1  5 g Medium MW Chloroform 1016 2.19  5* PM-2 S-2  5 g Medium MW Chloroform 10 16 4.21  6* PM-3  10 gMedium MW  25 ml chloroform 10 27 2.77  7* PM-5  5 g Medium MW  25methylene chloride 5 28 2.07  8 PM-6 Lot 1  10 g Low MW  50 ml methylenechloride 10 26 1.48  9 PM-6 Lot 2  10 g Low MW  50 ml methylene chloride10 24 1.35 10 PM-7  20 g Low MW  50 ml methylene chloride 20 40 1.31 11PM-8  20 g Medium MW 100 ml methylene chloride 20 48 1.54 12 PM-11  40 gLow MW 100 ml chloroform 40 47.5 0.52 13 PM-12  40 g Medium MW 200 mlchloroform 40 94 1.14 14 PM-13  40 g Low MW 100 ml chloroform 40 99 1.3415 PM-14  40 g 120K MW 125 ml chloroform 40 42 1.32 16 PM-15  60 g LowMW 150 ml methylene chloride 60 48 1.07 17 PM-16  60 g High MW 200 mlchloroform 60 91.5 1.39 18 PM-l7 Lot 1  10 g Low MW  25 ml chloroform 1074 1.43 19 PM-l7 Lot 2  30 g Low MW  75 ml chloroform 30 104 1.42 20PM-18 Lot 1 120 g High MW 455 ml chloroform 120 120 1.41 21 PM-19 Lot 1 10 g Low MW  25 ml chloroform 10 96 1.85 22 PM-19 Lot 2  20 g Low MW 50 ml chloroform 20 105 1.41 23 PM-20 Lot 1 120 g High MW 450 mlchloroform 120 96 1.45

EXAMPLE 24 Phosphonylated PMMA Reacted with Hydroxyethyl Methacrylate

[0033] A two-neck 250 ml boiling flask containing a magnetic stir barwas assembled with a condenser in one inlet and a gas inlet tube in theother. The set up was flame dried under vacuum and cooled to roomtemperature under argon purge twice. Thirty grams of low molecularweight polymethyl methacrylate (PMMA) and 75 ml chloroform was added tothe boiling flask. Once the PMMA was completely dissolved, 15 mlphosphorus trichloride was added to the solution. Oxygen was bubbledthrough the solution at 30 ml/min while stirring with the magnetic stirbar. The oxygen flow and stirring were continued at ambient temperaturefor 71 hours.

[0034] The condenser and gas inlet tube were removed from the flask andreplaced with a full length glass stopper and distillation arm connectedto a collection flask. The system was placed under vacuum at 50° C.while stirring to remove the chloroform. Once the solvent was removed,the flask was purged flask with argon and 60 ml chloroform was added todissolve the material in the flask. After the residue was dissolved, 6.1ml 2-hydroxyethyl methacrylate was added to the solution. After 5 days,the solution was precipitated by blending in distilled ice water. Themixture was left to settle in beakers and the water was then decanted.The solid portion was then transferred to a 2 L resin kettle and placedunder vacuum to remove chloroform. The solid portion was rinsed severaltimes with distilled water through vacuum filtration. Collectedprecipitate and dried under vacuum at 37° C.

[0035] The product contained 1.30% phosphorus and 1.16% chlorine and hada molecular weight of 9,023.

EXAMPLE 25 Phosphonylated PMMA Reacted with Glycidyl Methacrylate

[0036] A two-neck 250 ml boiling flask containing a magnetic stir barwas assembled with a 90° angle connector with stopcock. The set up wastwice flame dried under vacuum and cooled to room temperature underargon purge. The following were then added to the flask: 5.0 g2-butanol; 3.0 g PM-14; 0.005 g 4-methoxyphenol; 0.0015 g1,4-diazabicyclo-[2,2,2]oxetane; 1.5 g glycidyl-methacrylate; 100 gethyl acetate; and 50 g methanol. A sample was removed for FTIR analysisprior to reacting. The mixture was then heated to 60° C. under positiveargon pressure for 48 hours.

[0037] The 90° angle connector with stopcock was removed from the flaskand connected to a distillation head and the assembly was heated to 70°C. under vacuum for 45 min. The remaining mixture was precipitatedblending in distilled ice water. The precipitate was collected byfiltering through a coarse Buchner funnel.

Example 26 Phosphonylated PMMA Reacted with Glycidylmethacrylate

[0038] A two-neck 250 ml boiling flask containing a magnetic stir barwas assembled with a 90° angle connector with stopcock. The set up wastwice flame dried under vacuum and cooled to room temperature underargon purge. The following were then added to the flask: 5.0 g2-butanol; 3.0 g PM-14; 0.005 g 4-methoxyphenol; 0.0015 g1,4-diazabicyclo-[2,2,2]oxtane; 1.5 g glycidylmethacrylate; 100 g ethylacetate; and 50 g methanol. A sample was removed for FTIR analysis priorto reacting. The mixture was then heated to 60° C. under positive argonpressure for 48 hours.

[0039] The 90° angle connector with stopcock was removed from the flaskand connected to a distillation head and the assembly was heated to 70°C. under vacuum for 45 min. The remaining mixture was precipitated byblending in distilled ice water. The precipitate was collected byfiltering through a coarse Buchner funnel.

Example 27 Calcium Salt of Phosphonylated PMMA of Example 21

[0040] The preparation and characterization of the calcium salt (tosimulate the reaction of the PPMMA reaction with Ca⁺² in the biologicenvironment) can be summarized as follows: 2% of PPMMA of Example 21 wasdissolved in ethanol then centrifuged (solubility was about 47%) to theclear solution, 5 drops of a 1M CaCl₂ solution were added, theprecipitate was centrifuged and washed twice with ethanol, then dried byvacuum for 4 days. SEM/EDX analyses of the resulting microparticles wereperformed for Ca, P, O, C, Cl.

EXAMPLE 28 Preparation of Dental Varnish

[0041] A tooth varnish was prepared by mixing 1.186 ml of a 2.5 mg/mlsolution of a 75/25 methyl methacrylate-methacrylic acid copolymer(MMA/MAA) in ethanol with 50 μl of 2.5 mg/ml solution of the PPMMA ofExample 23 in ethanol in a sterile centrifuge tube. To this, 4 μl of a2.5 mg/ml solution of chlorhexadine diacetate in ethanol was added toyield a final concentration of 0.1 μg/15 μl.

EXAMPLE 29 Preparation of Dental Varnish

[0042] For this, a procedure similar to that used in Example 28 wasfollowed with the exception of substituting the 75/25 MMA/MAA copolymerwith its 67/33 analog to yield a final concentration of 3.75 μg/15 μl.

EXAMPLE 30 Coating of Porcelain and Bovine Teeth as Models for Dentine

[0043] Porcelain and precut, scoured teeth were sanded with a fine-gradesand paper. Both substrates were rinsed thoroughly with isopropylalcohol and dried at room temperature for 48 hours prior to use.Triplicate samples of both porcelain or bovine teeth were then coatedwith the dental varnish of Examples 28 or 29 to reach the desiredconcentration.

EXAMPLE 31 Drug Release Evaluation of Coated Porcelain

[0044] Porcelain chips from Example 30 were coated with a formulation ofExample 28 and placed in separate glass vials with 1 ml of distilledwater. The containers were then capped and placed in a 37° C. incubator.Aliquots were taken at various periods of time and analyzed by HPLCusing a 20-80% acetonitrile gradient and a C18 column and UV detector(220 nm). After 30 hours of incubation at 37° C., a total of 0.6 μg or1.5% of the total drug loading was released.

EXAMPLE 32 Drug Release Evaluation of Coated Teeth

[0045] The bovine teeth described in Example 30, which were coated withthe formulation of Example 29, were evaluated in a similar manner asdescribed in Example 31. The results indicate that 70% of the drug isreleased at 3 days.

[0046] The foregoing description of preferred embodiments of theinvention has been presented for illustration, and is not intended to beexhaustive. Modifications are possible in light of the above teachingsor may be acquired from practice of the invention.

What is claimed is:
 1. A randomly phosphonylated acrylate polymericcomposition comprising: an acrylic polymer; and phosphorous-containingfunctional groups, wherein the phosphorous atom of each functional groupis covalently bonded to a carbon atom of the acrylic polymer and whereinthe phosphorous atoms comprise at least about 0.1 percent by weight ofthe polymeric composition.
 2. The polymeric composition of claim 1wherein the acrylic polymer is polymethyl-methacrylate.
 3. The polymericcomposition of claim 2 wherein the phosphorous atoms comprise at least0.5 percent by weight of the polymeric composition.
 4. The polymericcomposition of claim 1 wherein the acrylic polymer comprisesmethyl-methacrylate and methacrylic acid-based repeat units.
 5. Thepolymeric composition of claim 4 wherein the phosphorous atoms compriseat least 0.5 percent by weight of the polymeric composition.
 6. Thepolymeric composition of claim 1 wherein an acrylic polymer comprises atleast one polymerizable side group per chain.
 7. The polymericcomposition of claim 6 wherein the polymerizable side group is derivedfrom a bis-acrylate monomer.
 8. The polymeric composition of claim 7wherein the bis-acrylate monomer comprises ethylene bis-methacrylate. 9.A dental product such as varnish or sealer comprising the polymericcomposition described in claims 1 through
 8. 10. The dental product ofclaim 9 further comprising fluoride ions.
 11. The dental product ofclaim 9 comprising bioactive compounds such as antimicrobials,anti-inflammatory drugs, or pain-relieving agents wherein the polymericcomposition is capable of regulating the release of said bioactivecompounds.
 12. A randomly phosphonylated polyalkylene oxide polymericcomposition comprising: a polyalkylene oxide polymer; andphosphorous-containing functional groups, wherein the phosphorous atomof each of the functional groups is covalently bonded to a carbon atomof the polyalkylene oxide polymer and wherein the phosphorous atomscomprise at least about 0.1 percent by weight of the polymericcomposition.
 13. The phosphonylated polyalkylene oxide polymericcomposition of claim 12 wherein the alkylene group comprises from two tosix carbon atoms.
 14. A randomly phosphonylated polyamide compositioncomprising: a polyamide polymer; and phosphorous-containing functionalgroups, wherein the phosphorous atom of each of the functional groups iscovalently bonded to a carbon atom of the polyamide polymer and whereinthe phosphorous atoms comprise at least about 0.1 percent by weight ofthe composition.
 15. The polyamide polymeric composition of claim 14wherein the polyamide polymer comprises the polymerization product ofN-alkyl laurolactam.
 16. A randomly phosphonylated polyester compositioncomprising: a polyester polymer; and phosphorous-containing functionalgroups, wherein the phosphorous atom of each of the functional groups iscovalently bonded to a carbon atom of the polyester polymer and whereinthe phosphorous atoms comprise at least about 0.1 percent by weight ofthe composition.
 17. The polyester composition of claim 16 wherein thepolyester polymer comprises poly-ε-caprolactone.
 18. The polyestercomposition of claim 16 wherein the phosphorous-containing functionalgroups comprise alkyl phosphonates.
 19. A flame retardant additive forpolyesters and polyurethane comprising the composition of claim
 18. 20.A polymer composition as in claims 1, 12, 14, or 16 further comprising abioactive compound linked to the phosphonyl functionality.